Overview of X-Ray Fluorescence Analysis AMPTEK, INC., Bedford, MA 01730 Ph: +1 781 275 2242 Fax: +1 781 275 3470 sales@amptek.com 1
What is X-Ray Fluorescence (XRF)? A physical process: Emission of characteristic "secondary" (or fluorescent) X-rays from a material that has been excited by high-energy X-rays or gamma rays. A technique in analytical chemistry: Method to identify elements in a sample and measure their concentrations Non-destructive, quick, and simple to carry out. 2
Physical Process Incoming radiation hits an atom Ejects an electron from an inner shell, creating a vacancy An electron from an outer shell drops down to fill the vacancy. The excited atom emits an X-ray with energy equal to the difference between the levels EXray = E = EK EL Since each element has a unique set of levels, it produces a unique set of characteristic X-rays 3
Physical Process Fe Ni Cu Zn Pb Atomic Levels K 1s 7,112 8,333 8,979 9,659 88,005 L 1 2s 845 1,009 1,097 1,196 15,861 L 2 2p 1/2 720 870 952 1,045 15,200 L 3 2p 3/2 707 853 933 1,022 13,035 M 1 3s 91 111 122 140 3,851 M 2 3p 1/2 53 68 77 91 3,554 M 3 3p 3/2 53 66 75 89 3,066 Characteristic X-Ray Lines K α1 K L 3 6,404 7,478 8,048 8,639 74,969 K α2 K L 2 6,391 7,461 8,028 8,616 72,804 K β1 K M 3 7,058 8,265 8,905 8,572 84,936 L α1 L 3 M 5 705 852 930 1,012 10,552 L α2 L 3 M 4 705 852 930 1,012 10,450 L β1 L 2 M 4 718 869 950 1,035 12,614 XRF is similar to optical spectroscopy but at higher energy Independent of chemical state Elemental analysis 4
Measurement Intensity of X-ray line proportional to number of atoms Quantitative X-rays pass through surface into sample Nondestructive and no sample preparation is necessary Best accuracy requires sample preparation Bulk measurement rather than only surface Notion of bulk vs surface depends on the X-ray energy 5
Measurement Iron Nickel Copper Zinc Brass (Cu/Zn alloy) Cu K α & K β Zn K α & K β Zn K α Cu K α Zn K α Cu K β Ni K α Ni K β Fe K α Fe K β 0 2 4 6 8 10 12 14 Presence of Cu and Zn K lines Elements are in sample (qualitative) Intensity of the lines How much is in sample (quantitative) 6
Measurement 7000 6000 Br K α RoHS/WEEE Reference Heavy Metals in PVC Blank Low High 5000 Cl K α Counts 4000 3000 Hg L α,l β,l γ Pb Lα,L β,l γ Cd K α 2000 1000 Cr K α Backscattered X-ray tube continuum 0 0 5 10 15 20 25 30 Typical spectrum and results Photopeak intensity varies with concentration Final result is quantitative concentration High Low Blank Certified XRF Cr 1000 + 20 895 + 198 Br 1100 + 22 1089 + 23 Cd 300 + 6 264 + 28 Hg 1100 + 22 1050 + 53 Pb 1200 + 24 1184 + 39 Cr 401 + 8 388 + 167 Br 500 + 10 487 + 13 Cd 100 + 5 68 + 13 Hg 200 + 5 183 + 27 Pb 400 + 8 398 + 23 Cr 0 + 5 7 + 40 Br 0 + 5 1 + 2 Cd 0 + 5 9 + 10 Hg 0 + 5 0 + 0 Pb 0 + 5 10 + 9 7
Measurement What are the main factors limiting XRF? Counting variance The measurement is based on count discrete X-rays Arise from random processes Inherent statistical variation in number of X-rays Percent uncertainty = 1/ N 100 X-rays detected 10% precision 1,000 X-rays detected 3% precision 1,000,000 X-rays 1000 ppm precision Good precision means many X-rays which means high count rates or long times Detector response Photopeak has some width There is always spectral background and overlapping peaks Ability to remove these depends on counting variance, energy resolution, and accuracy of software algorithms Better energy resolution helps but there are physical and practical limits 8
Measurement What are the main factors limiting XRF? Attenuation lengths Penetration depth depends on energy & therefore element In silica, Al X-rays go 3 µm while Sn go 3 mm Response depends on energy/element Sample condition & homogeneity are critical 1.0E+01 Atten length silica (cm) 1.0E+00 1.0E-01 1.0E-02 1.0E-03 1 cm 1 mm 0.1 mm 10 micron 1.0E-04 Mg Al Si P S Cl Ca Cr Fe Ni Zn As Br Zr Ag Sn Ba Sm W Pb U 1 10 100 9
Measurement FAQ How accurate is EDXRF? In the best case, relative accuracy ~ 0.2% (1.00% + 20 ppm). Requires sample prep, a known matrix, good statistics, etc Nondestructive screening, relative accuracy ~ 2% (1.00 + 0.02%) Requires careful optimize and setup, known sample type Quick check on unknown, relative accuracy ~20% (1.0 + 0.2 %) What is the detection limit for EDXRF? <1 ppm for prepared samples in a known matrix under good conditions 10 ppm in nondestructive screening with no interfering elements When elements interference or overlap, 1% of other element What elements can be analyzed with EDXRF? Na to U (down to Be with EDS) Low Z elements (below S) are a challenge Need multiple measurements to cover a wide range of elements 10
Measurement XRF is one of many methods used in material analysis Advantages of XRF Non-destructive No sample preparation Fast (seconds to minutes) Good precision and accuracy Measure Na to U Suitable for portable equipment and field use Disadvantages of XRF Limits of detection modest (10 ppm typical) Accuracy usually modest (few % relative) Difficult to use for lower Z elements Best results require Sample preparation (damaging) System optimization Matched calibration standards 11
XRF Applications How is XRF used? 12
Hazardous Material Screening Is there cadmium on this toy? Is there lead in this paint? Does this circuit board contain Pb, Cd, or Cr? Nondestructive critical for screening products! 3,500 3,000 Cu K α Br K α Amptek SDD "Pb free" circuit board 3,000 2,500 Pb L α & L β & L γ Lead paint on wood 2,000 Ti K α Amptek SDD Cd painted PVC 2,500 2,000 1,500 Cr K α Fe K α Cd K α & K β Counts 2,000 1,500 Pb L α & L β Ag K α Sn K α Counts 1,500 Ca K α Ti K α Zn K α Counts 1,000 Cl K α 1,000 1,000 500 500 500 0 0 5 10 15 20 25 30 35 40 0 0 5 10 15 20 25 30 0 0 5 10 15 20 25 30 35 40 13
Metal Alloy Analysis Are these bolts stainless steel 316? Is there Ni in this scrap metal? Is there Cd plating on this MILSPEC connector? How much Au is in a white gold ring? Speed critical, accuracy moderate Counts 4,500 4,000 3,500 3,000 2,500 2,000 1,500 1,000 500 Cu K α Zn K α Au L α & L β & L γ Gold plated High-rel connector 0 0 5 10 15 20 25 30 40,000 35,000 30,000 Fe K α Stainless steel 316 2,500 2,000 Cu K α Au L α & L β & L γ White gold ring Zn K α 25,000 1,500 Ni K α Counts 20,000 15,000 Counts 1,000 Cr K α 10,000 Mo K α 500 5,000 Ni K α 0 0 5 10 15 20 25 30 0 0 5 10 15 20 25 30 35 40 14
Art and Archeology How did the artist make their paints? Is this an ancient or a modern pigment? What is the effect of cleaning on the surface of a statue? Nondestructive testing is vital for art! 15
Process Control Is there any change in spectrum? Multilayer metal Absolute composition not needed but quick, real-time, non-destructive vital. 16
Field Measurements Measuring ores in mines. Identifying minerals on Mars. 3.0E+04 Ca K α Fe K α Amptek FastSDD Rare Earth Ore 2.0E+04 Sr K α Counts 1.0E+04 Pb L lines Backscatter from X-ray tube La K α Ce Kα 0.0E+00 0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 Measuring soil contamination 17
Related Analytical Methods 18
Related Energy Dispersive X-ray Spectroscopy a.k.a. EDS, EDX, XEDS, EDXA Uses electron beam in vacuum chamber to excite the atoms Electrons have short range in matter Only way to measure lightest elements, down to Be (Z of 4) High spatial resolution (75 um spatial, 1 um in depth) 1.0E+05 8.0E+04 Be K α Amptek FastSDD Counts 6.0E+04 4.0E+04 C K α O K α 2.0E+04 Al K α 0.0E+00 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 19
Related Wavelength Dispersive X-ray Spectroscopy (WDXRF) Crystal diffractometer disperses the X-ray wavelengths much like a prism disperses visible light. X-rays at a particular wavelength (energy) are recorded by a detector. It measures only one energy at a time; It obtains a spectrum by sweeping the wavelength over time Advantages of WDXRF Much better energy resolution Leads to much better accuracy and detection limits Disadvantage of WDXRF Very long time to acquire whole spectrum Requires destructive sample preparation Uses similar detectors and signal processors 20